P
US7087641B2ExpiredUtilityPatentIndex 71

4β-1″-[(2″-substituted benzoyl) anilino]podophyllotoxin analogues useful as anticancer agents

Assignee: COUNCIL SCIENT IND RESPriority: Mar 28, 2002Filed: Mar 28, 2002Granted: Aug 8, 2006
Est. expiryMar 28, 2022(expired)· nominal 20-yr term from priority
Inventors:KAMAL AHMEDREDDY PERAM SURAKATTULA MURALI
C07D 493/04A61P 35/00
71
PatentIndex Score
8
Cited by
7
References
21
Claims

Abstract

The present invention provides a new class of compounds 4β-1″-[{2″-benzoyl substituted}anilino] podophyllotoxin exhibiting anti cancer activity and a process for preparing the same.

Claims

exact text as granted — not AI-modified
1. Analogs of 4β-1″-[{2″-benzoyl substituted}anilino] podophyllotoxin of compound 2 
       
         
           
           
               
               
           
         
         wherein R, R 1  and R 2  independently or in combination represents 
         R=H or CH 3    
         R 1 =H or halogen 
         R 2 =H, NO 2  or halogen. 
       
     
     
       2. Analogs of 4β-1″-[{2″-benzoyl substituted}anilino] podophyllotoxin as claimed in  claim 1  selected from the group consisting of: 
       
         
           
                 
                 
                 
                 
                 
                 
               
                     
                     
                 
                     
                   S. No 
                   R 
                   R 1   
                   R 2   
                   GI 50  μM 
                 
                     
                     
                 
                     
                   4a 
                   CH 3   
                   H 
                   H 
                   0.04–0.5  
                 
                     
                   4b 
                   H 
                   H 
                   H 
                    15–382 
                 
                     
                   4c 
                   CH 3   
                   2-Cl 
                   4-Cl 
                   0.059–0.876 
                 
                     
                   4d 
                   H 
                   2-Cl 
                   4-Cl 
                    0.1–0.24 
                 
                     
                   4e 
                   CH 3   
                   H 
                   4-NO 2   
                   <10 nM–0.28      
                 
                     
                   4f 
                   H 
                   H 
                   4-NO 2   
                   0.01–0.24 
                 
                     
                   4g 
                   CH 3   
                   H 
                   4-Cl 
                   0.07–1.1  
                 
                     
                   4h 
                   H 
                   H 
                   4-Cl 
                    14–270 
                 
                     
                   4I 
                   CH 3   
                   2-F 
                   4-Cl 
                   0.14–0.3  
                 
                     
                   4j 
                   H 
                   2-F 
                   4-Cl 
                   0.004–0.1  
                 
                     
                   4k 
                   CH 3   
                   H 
                   H 
                   0.1–1   
                 
                     
                   4l 
                   H 
                   H 
                   H 
                    2–16 
                 
                     
                   4m 
                   CH 3   
                   H 
                   4-NO 2   
                   0.01–0.2  
                 
                     
                   4n 
                   H 
                   H 
                   4-NO 2   
                   0.01–0.24 
                 
                     
                   4o 
                   CH 3   
                   H 
                   4-NH 2   
                   0.04–1   
                 
                     
                   4p 
                   H 
                   H 
                   4-NH 2   
                   0.015–0.4 . 
                 
                     
                     
                 
             
                
                
                
               
               
                
                
                
                
                
                
                
                
                
                
                
                
                
                
                
                
                
               
            
           
         
       
     
     
       3. A process for the preparation of 4β-1″-[{2″-benzoyl substituted}anilino] podophyllotoxin analogs of Compound 2 
       
         
           
           
               
               
           
         
         wherein R, R 1  and R 2  independently or in combination represents 
         R=H or CH 3    
         R 1 =H or halogen 
         R 2 =H, NO 2  or halogen 
         the process comprising the following steps: 
         a) reacting 4β-bromo-4-dioxypodophyllotoxin with substituted or unsubstituted 2-aminobenzophenone in presence of phase transfer catalyst, base in an anhydrous organic solvent medium at a temperature ranging between −10° to 40° C. for 4–16 hours, 
         b) removing the organic solvent from the reaction mixture of step (a) under reduced pressure to obtain a residue, and 
         c) purifying the residue of step (b) over silica gel column, eluting with mixture of chloroform-methanol to obtain the required 4β-1″-[{2″-benzoyl substituted}anilino] podophyllotoxin analogs. 
       
     
     
       4. A process as claimed in  claim 3  wherein in step (a), the phase transfer catalyst used is selected from a group consisting of tetrabutyl ammonium chloride, tetrabutyl ammonium bromide, tetra butyl ammonium iodide or aliquat 336. 
     
     
       5. A process as claimed in  claim 3  wherein in step (a), the substituted 2-amino benzophenone are selected from group consisting of 2-amino-2′, 5′-dichlorobenzophenone, 2-amino-5-nitrobenzophenone, 2-amino-5-chlorobenzophenone, 2-amino-5-chlorobenzophenone, 2-amino-5-chloro-2′-fluorobenzophenone, 2-amino-4′bromobenzophenone, and 4-amino-3-nitrobenzophenone. 
     
     
       6. A process as claimed in  claim 3  wherein in step (a), the organic solvent used is selected from group consisting of dichlorormethane, chloroform, tetrahydrofuran or dioxane. 
     
     
       7. A process as claimed in  claim 3  wherein in step (a), the base used is selected from group consisting of trimethylamine, triethylamine, sodium carbonate, potassium carbonate, cesium carbonate and barium carbonate. 
     
     
       8. A process as claimed in  claim 3  wherein the reaction is carried out at room temperature. 
     
     
       9. A process as claimed in  claim 3  wherein in step (a), the molar ratio of substituted or unsubstituted benzophenone and the bromocompound used is in the range of 1:1 to 2:1 and preferably 1:1.17. 
     
     
       10. A process as claimed in  claim 3  wherein in step (a), the mole equivalent ratio of bromo compound to phase transfer catalyst is in the range of 1:0.2 to 1:0.5. 
     
     
       11. A method for treating cancer in a subject in need thereof comprising administering a pharmaceutically effective dosage of 4β-1″-[{2″-benzoyl substituted}anilino] podophyllotoxin analogues of general formula (2) as claimed in  claim 1 . 
     
     
       12. A method as claimed in  claim 11  wherein 4β-1″-[{2″-benzoyl substituted}anilino] podophyllotoxin analogs are used singly or in combination with each other. 
     
     
       13. A method as claimed in  claim 11  wherein the analogs of general formula (2) are administered systemically or orally. 
     
     
       14. A method as claimed in  claim 11  wherein the subject is a mammal. 
     
     
       15. A method as claimed in  claim 14  wherein the subject is a human. 
     
     
       16. A method as claimed in  claim 11 , wherein the compound of general formula (2) is administered to the subject in combination with pharmaceutically acceptable additives, carriers, diluent, solvent, filter, lubricant, excipient, binder or stabilizer. 
     
     
       17. A method as claimed in  claim 11  wherein the GI 50 value of in vitro anti-cancer activity of preferred analogs is in the range of 0.001–382. 
     
     
       18. A process as claimed in  claim 4 , wherein the phase transfer catalyst is tetrabutylammonium iodide. 
     
     
       19. A process as claimed in  claim 7 , wherein the organic solvent is tetrahydrofuran. 
     
     
       20. A process as claimed in  claim 8 , wherein the base is triethylamine. 
     
     
       21. A process as claimed in  claim 9 , wherein the molar ratio is 1:1.17.

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